Thermodynamics for Cryogenics

with the emphasis here on large-scale helium cryogenics

Tom Peterson, SLAC

January 2017
 Outline
• Definitions
• Perfect gas (Pv=RT)
• Equations of state
• Entropy
• Compression and expansion processes
• Liquid/vapor systems

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 Old science with modern applications
• Thermodynamics is the
study of macroscopic
energy transformations
between heat and work
• Thermodynamics has its
basis in attempts to
understand combustion
and steam power (much
in the 19th century) but
is still “state of the art”
in terms of practical
engineering issues for
James Dewar (invented vacuum flask in
cryogenics 1892)
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 Focus of this lecture
• Thermodynamics is a large area of study,
far too much to cover in this one-hour
introduction
• I will focus on the thermodynamics
concepts which I have found most
important in my experience designing
cryogenic systems and cryostats

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 The laws of thermodynamics
• First law – “The energy of the isolated system is
conserved.” (Conservation of energy)
• Second law – “The entropy of the isolated system
increases in all real processes and is conserved in
reversible (theoretical) processes.”
• Third law – “The entropy of a pure substance in
complete thermodynamic equilibrium becomes
zero at a temperature of absolute zero.” (One can
never reach absolute zero.)

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Some thermodynamics definitions
• A “system” in thermodynamics is a
specified region in which mass transfer
and/or heat transfer is studied
– A “boundary” separates the system from its
“surroundings”
– Proper definition of the system can be
important in solving a problem (we’ll see that
in some examples later)

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 More definitions
• An “isolated” system has no mass or energy crossing the
boundary
• A “closed” system has no mass crossing the boundary
• An “open” system has mass crossing the boundary and
may or may not have constant mass
• The thermodynamic “state” of the system is the condition
at a moment in time as defined by the system properties
• In general, two properties define the state of a system
consisting of a pure substance in equilibrium

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 Commonly used properties
• T – temperature
• P – pressure (force per unit area)
• v – specific volume (volume V per unit mass)
• U – internal energy of the closed system or
• u – internal energy per unit mass
• H – enthalpy = U + PV
• h – enthalpy per unit mass (specific enthalpy)
• S – entropy
• s – entropy per unit mass

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 Derived properties, Cv , Cp , k
• Some important thermodynamic properties are defined
from others, such as the heat capacities, cv , and cP , and k
¶U ö ¶H ö cP
cv º ÷ cp º ÷ kº
¶T øV ¶T øP cv
• Since typically two properties define the state of the pure
fluid in thermodynamics, equations generally have two
independent variables
• Derivatives then are partial derivatives with respect to one
independent variable with the other held constant

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 Perfect gas approximation
• A perfect gas obeys the equation Pv=RT where R is a
constant called the gas constant
• The internal energy of a perfect gas is a function of
temperature alone, Du = cv DT where cv is constant
• Since h = u +Pv, so h = u + RT for a perfect gas, enthalpy
is also a function of temperature alone for a perfect gas,
where cp is constant. Dh = c p DT

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 Pv/RT versus P for helium

Pv/RT
300 K

20 K

Pressure (atm)
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 Equations of State
• In many cases, Pv=RT may be a good approximation
– For example, far enough from the critical pressure and from the
condensation temperature
– Good to within 10% for helium down to 8 K
• Terms may be added to account for deviations from
Pv=RT, such as Pv B C D
=1+ + + +....
RT v v 2
v 3

• This is called the “virial equation”, and the coefficients B,

C, etc. are called “virial coefficients”.
• Equations of state enable calculation of fluid properties
based on measurements of some of the basic properties
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 Helium phase
diagram
(Steven W. VanSciver,
Helium Cryogenics, p. 54)

• Critical point is 5.2 K,

2.245 atm
• Lambda transition
from helum I to
helium II is 2.172 K

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From Obert,
Concepts of
Thermodynamics

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 Entropy
• Least intuitive of the common properties
• Definition of entropy is based on energy change in
a perfect, loss-free (reversible) process
dQrev
dS =
T
• Entropy is the property which is held constant in a
adiabatic (no heat flow in or out) reversible
process like the perfect closed piston compression
and expansion
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 T-s
diagram for
helium

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 The TdS equations
• From the first law (energy conservation) for a
closed system with reversible addition or removal
of heat and mechanical work (pdV), we have:
dQrev = dU + PdV
• With dQrev = TdS we have the first TdS equation:
TdS = dU + PdV
• From H =U + PV dH = dU + PdV +VdP
• Which gives us the second TdS equation:
TdS = dH -VdP
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 Isothermal compression
Example application of TdS equation
• From the second TdS equation, TdS = dH -VdP
with constant temperature (isothermal) compression of an
ideal gas, dH = 0, so TdS = -VdP
• For the ideal gas, PV = RT = const
• substituting V = RT P gives

dP
TdS = -RT and integrating,
P
TDs = RT ´ ln ( Pout Pin )

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 Isothermal compression
• Isothermal compression “squeezes” the entropy out of the
helium by increasing pressure at constant temperature
• Enthalpy h (function of T alone) remains constant
• Yet energy (heat) is removed in isothermal compression
• That energy is DQ = TDs and is equal to the compressor
work, which we saw is TDs = RT ´ ln ( Pout Pin )

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 Isothermal compression example
• The second stage screw compressor at Fermilab’s
MTF compresses 200 grams/sec helium from
about 2.6 bar to 15 bar
• For helium R = 2.078 J/gK, so the ideal work at
300 K would be
æ J ö æ 15 öæ grams ö
ç 2.078 ÷ (300K ) ln ç ÷ç 200 ÷ = 220kW
è gK ø è 2.6 øè sec ø

• With typical power consumption of 800 HP = 600

kW, the isothermal efficiency is about 37%
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 A real helium compressor
• Oil-flooded screw compressors are now standard
• A typical pressure ratio is about 4:1, so two stages
are used in a typical helium plant to get a 15:1 to
20 :1 pressure ratio

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 Isentropic expansion
• Removes energy from the system at
constant entropy by means of adiabatic (no
heat transfer) reversible (loss-free) work
• Expansion at constant entropy from about
70,000 atm and room temperature to 1 atm
would remove enthalpy (as work) to that of
2-phase helium

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 Isentropic efficiency
• Isentropic expansion efficiency is defined as
Dhreal
Dhisentropc
• where Δh = hin – hout
• Δhreal will always be less than Δhisentropc so
efficiency will be less than 100%
• For real expanders, 65% to 85%

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 Ideal helium process
Work in = TambDs Work out = Dh
Heat out

Isothermal Isentropic
Compressor Expander
Heat in = Dh

Return Product
Load

Net ideal work in = T ambDs - Dh

(in dimension of energy per unit mass)
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 Isothermal heat absorption
• Net ideal work (energy per unit mass of working
fluid) into the system is Tambs- h
• For a refrigerator with the heat load absorbed by
evaporation at constant liquid temperature, Tliq,
h = Tliq s
• Thus, the ratio of applied work to heat absorbed is
(Tamb s- h)/ h = Tamb/Tliq-1
• For low temperatures this is approximately the
ratio of absolute temperatures, Tamb/Tl

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 Power required for a non-
isothermal load

• Use
• Where P is the ideal room-temperature
power required to remove a non-isothermal
heat load
• I will show the use of this later in
calculating cryogenic system power

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 Exergy
• In many cryogenics analyses, authors
describe an “exergy” analysis
– Exergy is defined as de = dh – T0ds, which is
the quantity described previously as the ideal
refrigeration power
– At each stage, one can compare the real power
required with expected, from

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 Gibbs Free Energy
• In thermodynamics texts, you will find the quantity Gibbs
Free Energy defined, which is G = H – TS
• For processes which start and end at the same temperature,
one may compare the real process with an ideal cycle
rejecting heat to that reference temperature, T0. On a per
unit mass basis, dg = dh – T0ds
• So exergy (the ideal work for refrigeration) is basically the
same concept in reverse as Gibbs Free Energy, the
maximum work that can be extracted from a process doing
work

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 Example cryo power analysis
• See ILCcryoTDP-26June2012.xls

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 Cryogenic plant losses (compressor)
from B. Ziegler, “Second Law Analysis of the Helium Refrigerators for the
HERA Proton Magnet Ring,” in Advances in Cryogenic Engineering,
Vol. 31, Plenum Press, 1986, p. 693

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 Cryogenic plant losses (cold box)
from B. Ziegler, “Second Law Analysis of the Helium Refrigerators for the
HERA Proton Magnet Ring,” in Advances in Cryogenic Engineering,
Vol. 31, Plenum Press, 1986, p. 693

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 Expansion engines
• Reciprocating expansion
engines are used in many
small liquefiers and help to
illustrate some fundamentals
of thermodynamics
• At the right is a Koch Process
Systems (similar to “model
1400”) expander with
cryostat open

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 Expansion engine cylinder
• At the right is a close-
up of the expander
showing the cylinder,
valve bodies, and some
of the cryogenic piping

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 Expansion engine cycle
Work extraction Work extraction

1 2 3 4 5

Minimal volume, Filling cylinder, Valves closed, Maximal volume, Cut-off volume,
intake valve then intake constant mass exhaust valve exhaust valve
opens valve closes expansion opens closes

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 Pressure trace
2

4 5

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 Efficiency discussion
• Intake cutoff, incomplete expansion
– Leaves some pressure unutilized
– Allows larger mass flow (intake valve open longer,
more mass into cylinder each stroke)
• Intake and discharge valve leakage
• Heat conduction into expander
• Heat transfer to and from cylinder walls and piston
head
• Dead volume leaves cooled helium behind which
mixes with intake
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 Helium expansion example

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 Isenthalpic expansion
• Expansion through a valve does no work, and
neither adds nor removes energy
– Process is isenthalpic
• Enthalpy of the perfect gas is a function of
temperature alone
¶T ö
– Isenthalpic process of perfect gas ÷ =0
does not change the temperature ¶P øh
• Real fluids may change temperature via an
isenthalpic expansion
– Joule-Thomson effect
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 Joule-Thomson expansion
• In many real fluids, including helium near
the liquid-vapor dome (see T-s diagram),
isenthalpic expansion may provide
temperature drop
– Not as efficient of isentropic expansion
– But very convenient and easy (no moving parts)
• Joule-Thomson expansion through a valve
is said to be through a “J-T valve”
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 T-s
diagram for
helium
(closer look)

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 Helium JT inversion curve
• Note that lines of constant enthalpy are not horizontal (not
constant temperature) on the previous T-s diagram.
• Movement along a line of constant enthalpy with a
pressure change (isenthalpic expansion or compression)
may result in a temperature increase or decrease.

dP ö dP ö
• The curve demarking where ÷ < 0 and where ÷ >0
dT øh dT øh

is called the “Joule-Thomson inversion curve”.

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 Turboexpander
• Linde turbine at right
• Expansion turbines are
typically used in
helium refrigerators
larger than about 500
W.
• Real efficiencies
(relative to isentropic)
are 60% to 80%

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 A simplified real helium cycle
Klaus D. Timmerhaus and Thomas M. Flynn,
Cryogenic Process Engineering, p.126

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A more typical modern helium cycle
(but still simplified, from Linde Kryotechnik, AG)
• The “Claude process”,
shown to the right,
includes intermediate
temperature expanders
• Modern cryoplants
follow this pattern
• The HERA plants
each have 7
turboexpanders

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 Cold box losses
from B. Ziegler, “Second Law Analysis of the Helium Refrigerators for
the HERA Proton Magnet Ring,” in Advances in Cryogenic Engineering,
Vol. 31, Plenum Press, 1986, p. 693

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 Helium cycle efficiency
RHIC CEBAF HERA LEP

Equivalent 25 13 8.4 per 6 per

capacity at coldbox coldbox
4.5K (KW)
Power 450 350 285 230
required in
W/W
Efficiency 16% 20% 25% 30%

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 References
• Edward F. Obert, Concepts of Thermodynamics, McGraw-
Hill, Inc., 1960.
• R. Byron Bird, Warren E. Stewart, Edwin N. Lightfoot,
Transport Phenomena, John Wiley &Sons, 1960.
• S. W. VanSciver, Helium Cryogenics, Plenum Press, 1986.
• Mooney, David A., Mechanical Engineering
Thermodynamics, Prentice-Hall, Inc., New York, 1953.

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Question for discussion
tomorrow
“Square wave engine”
 Square wave engine
illustrates an interesting thermodynamics problem
• “Square wave” engine problem
– Suppose intake valve is open for entire 180 degree
intake stroke
– No closed-cylinder expansion
– Intake valve closes, then exhaust valve opens, so
cylinder contents blow down from intake pressure to
discharge pressure

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 Intake valve open 180 degrees
Fill cylinder with intake valve open, then open exhaust valve

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 Square wave pressure trace

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 Square wave problem
• Entire intake stroke at higher pressure than
entire discharge stroke
• Engine clearly does work, generates power
• But no isentropic expansion
– No closed-cylinder expansion of any kind
• Where does power come from? What gas
properties change, and how? We’ll discuss
that tomorrow.
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